Cationic (Charge Shift) Exciplexes.

Of the many known examples of exciplexes, those formed from bimolecular encounter between a cationic, excited state electron acceptor and a neutral donor in fluid media have not been previously reported. We now show that emissive exciplexes formed from excited N-methyl isoquinolinium cation (NMiQ+ ) with alkyl benzene donors are readily detected in acetonitrile. These cationic exciplexes result in a charge shift (A+ * + D → A• D•+ ) with no net change in charge, which differs fundamentally from the charge-generation of conventional exciplex formation (A* + D → A•- D•+ ). We find that cationic and conventional exciplexes show similar trends, e.g., bathochromic shifts and decreases in fluorescence quantum yields with decreasing oxidation potentials of the donors. In the presented examples of NMiQ+ exciplexes, the fluorescence quantum yield decreases by a factor of 30 and the radiative rate constant by 6.6 as the fractional CT character of the exciplex increases from ∼0.79 to ∼0.95. Interestingly, the electronic coupling matrix elements for the NMiQ+ exciplexes, derived from a correlation of the radiative rate constants with the average emission frequencies, are similar to those of related conventional exciplexes, in spite of the absence of Coulombic stabilization in the cationic exciplexes.